Preparation of Heat Resistant Oxide Coatings by the Sol-Gel Process and Their Application to Surface Modification of Metal Sheets

以金属醇盐为原料的溶胶-凝胶法是制备涂层的主要工艺之一。本研究的目的是发展溶胶-凝胶法在金属表面涂覆氧化膜，从而对其表面进行改性。取得了以下研究成果：1.在SiO_2涂层中引入甲基，可以弯曲和压制金属衬底，而不会使涂层剥落。用铬酸和硫酸溶液对衬底进行前处理，由于氧化层的形成，提高了SiO_2涂层在金属表面的附着力。以辛酸锆为原料，在金属板材上连续镀制了氧化锆薄膜。此外，氟离子的掺入使薄膜具有良好的拒水性能。高水解性金属醇盐，如铝醇盐，用β-二酮和胺稳定。然而，稳定剂的效果很大程度上依赖于溶剂。以乙酰丙酮稳定的钛、锆醇氧化物为原料，在常压下制备了PbTiO3-PbZRO_3铁电薄膜。考察了MO-B&lt；@D22@&gt；D2O&lt；@D23@&gt；D2-SiO&lt；@D22@&gt；D2(M=镁、锌)和P&lt；@D22@&gt；D2O&lt；@D25@&gt；D2-B&lt；@D22@&gt；D2O&lt；@23@&gt；D2-SiO&lt；@D22@&gt；D2体系钝化膜的制备条件。研究还发现，TiO系的薄膜对玻璃基板具有良好的耐候性。在二氧化钛-二氧化硅溶胶中加入有机聚合物可以延缓凝胶的凝胶化，并可在其上形成精细图案化的凝胶薄膜。这一发现可以应用于玻璃基板上预制槽的形成。以锂钛醇盐和磷酸为原料，在较低温度下合成了离子导电化合物LiTi2(PO4)3。含有H_3PMo_2；12&gt；O_&lt；40&gt；的SiO_2薄膜也具有较高的质子导电性。

The sol-gel process, which starts from metal-alkoxides, is one of the pomising processes for the preparation of coating films. This research project was carried out to develop the sol-gel process for the coating of oxide films on metal substrates and thereby to modify the properties of their surfaces. The following results were obtained.1. The incorporation of methyl groups into SiO_2 coatings enabled to bend and press metal substrates without pealing of the coatings. The pre-treatment of the substrates with a solution of chromic acid and sulfuric acid improved the adhesion of SiO_2 coatings on the metal surfaces due to the formation of oxide layers.2. ZrO_2 films were continuously coated on metal sheets using zirconium octylates as starting materials. Moreover, the incorporation of fluorine into ZrO_2 films brought about the good water repellency.3. Highly hydrolyzable metal alkoxides, such as Al-alkoxides, were stabilized with beta-diketones and amines. The effects of stabilizer were however found to be greatly dependent on solvents.4. PbTiO_3 -pbzro_3 ferroelectric films were prepared in an ambient atmosphere from alkoxides of Ti and Zr stabilized with acetylacetone.5. Preparation conditions of passivation films in the MO-B<@D22@>D2O<@D23@>D2-SiO<@D22@>D2 (M=Mg, Zn) and P<@D22@>D2O<@D25@>D2-B<@D22@>D2O<@23@>D2-SiO<@D22@>D2 systems were examined. The films in the TiO<@D22@>D2-SiO<@D22@>D2 system were also found to have good weathering-resistance for glass substrates.6. The addition of organic polymers to TiO_2-SiO_2 sols retarded the gelation and gave the gel films on which fine-patterning was possible with a stamper. This finding can be applied to the formation of pregrooves on glass substrates.7. Ionic-conducting compound LiTi_2(PO_4)_3 was prepared at relatively low temperatures from alkoxides of Li and Ti and phosphoric acid. SiO_2 films containing H_3PMO_<12>O_<40> were also found to show a high proton-conduction.